CN108160033B - Preparation method of activated clay reinforced ultra-light foam carbon - Google Patents
Preparation method of activated clay reinforced ultra-light foam carbon Download PDFInfo
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- CN108160033B CN108160033B CN201810007659.8A CN201810007659A CN108160033B CN 108160033 B CN108160033 B CN 108160033B CN 201810007659 A CN201810007659 A CN 201810007659A CN 108160033 B CN108160033 B CN 108160033B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
Abstract
The invention relates to a preparation method of activated clay reinforced ultralight foam carbon. The method comprises the following steps: (1) putting the purified natural nano clay mineral into a container, adding hydrochloric acid for acidification treatment, and rapidly activating and loosening by microwave to obtain acid-activated nano clay mineral powder; (2) placing the acid-activated nano clay powder and a phenol derivative in a reaction kettle, adding nitric acid, preserving the temperature for 1-2 hours at the temperature of 100-120 ℃, and adding concentrated sulfuric acid and ammonium sulfate to obtain sulfonated gel; (3) and placing the obtained sulfonated gel into a porcelain boat, placing the porcelain boat into an atmosphere microwave tube furnace, and carrying out heat preservation and carbonization for 3-5 min at the temperature of 800-1200 ℃ to finally obtain the nano clay mineral reinforced foam carbon composite material. The composite foamy carbon material obtained by the invention has the advantages of small density, large specific surface area, good adsorption performance, excellent performance particularly in the aspect of separation and purification of oily wastewater, low cost of raw materials and wide source.
Description
Technical Field
The invention relates to a preparation method of an ultralight foam carbon composite material reinforced by natural nano clay minerals, belonging to the field of composite material preparation.
Background
The foam carbon has the characteristics of low density, large specific surface area, strong adsorption capacity, high temperature resistance, high heat conductivity, electric conductivity and the like, is widely used as a supercapacitor, a catalyst carrier, a heat exchanger, an electrode material and the like, and in the aspect of environmental management, the foam carbon is also widely used for adsorption and purification treatment of sewage such as oil stains, heavy metal ions, organic pollutants and the like, the related patents for the preparation of the foam carbon are numerous, such as Z L, 201410378018.5, Z L, 201310004952.6, CN105272256A, Z L, 201310527246, X, CN106976863A and the like, the foam asphalt is generated by foaming asphalt or phenolic resin serving as a raw material, and then is impregnated and carbonized or graphitized, or the foam carbon is directly mixed with a foaming agent, a catalyst and the like by using an organic matter for modification, solidification or microwave foaming, and finally carbonized to prepare the foam carbon with uniform pore diameter, but the process is complex, including foaming, solidification, carbonization or graphitization and the like, not only is long in time consuming, high in energy consumption, and easy to generate pollutants, especially when the phenolic resin is used as a raw material for preparing a raw material for a carbon material for preparing a composite diesel oil, the foam carbon-based carbon nano carbon is prepared by directly absorbing the high-carbon nano carbon material, the high-carbon nano carbon material prepared by directly absorbing graphite-oil, the high-oil, the micro-oil-graphite-carbon nano-oil, the micro-oil adsorption-oil-carbon material prepared by directly absorbing material, the micro-graphite-oil-graphite-carbon nano-oil-carbon nano-carbon material is not suitable for the micro-oil adsorption, the micro-oil adsorption-oil-carbon nano-oil adsorption-oil adsorption-oil-carbon material, the micro-oil-carbon nano-oil-carbon nano-oil-.
The patent uses the abundant, low-cost porous or lamellar structure purified natural nano clay mineral as the reinforcing material to develop the natural nano clay mineral with the density lower than 0.02g/cm3The natural nano clay mineral reinforced foam carbon composite material fully exerts the unique structure, huge specific surface area and excellent adsorption performance of the clay mineral, and optimizes the oil stain adsorption and sewage purification functions of the foam carbon while enhancing the mechanical stability of the foam carbon. Meanwhile, the preparation process combining the clay mineral and the foam carbon has the advantages of simple process, low cost, large-scale industrial production, efficient and reasonable utilization of cheap mineral resources and excellent environmental management performance.
Disclosure of Invention
The invention aims to provide a preparation method of activated clay reinforced ultra-light foam carbon, aiming at the defects in the prior art. The method uses purified natural nano clay mineral as a reinforcement, uses a phenol derivative raw material as a carbon source, grafts active functional groups on OH-groups in situ through a unique process of nitration first and sulfonation later, and finally prepares the ultra-light foam carbon composite material through microwave rapid foaming and carbonization treatment processes of sulfonated gel. The composite foamy carbon material obtained by the invention has the advantages of small density, large specific surface area, good adsorption performance, excellent performance particularly in the aspect of separation and purification of oily wastewater, low cost of raw materials and wide source.
A preparation method of activated clay reinforced ultralight foam carbon comprises the following steps:
(1) activating the purified nano clay mineral, namely putting the purified natural nano clay mineral into a container, adding 0.5-2 mol/L hydrochloric acid, stirring at a high speed, performing ultrasonic dispersion, stirring and ultrasonic dispersion treatment, and performing suction filtration to obtain a filter cake, performing microwave rapid activation and loosening on the filter cake, repeatedly washing the filter cake with deionized water until the filter cake is neutral, finally drying the filter cake for 24 hours in a drying oven at 70-80 ℃, performing ball milling and crushing to obtain acid-activated nano clay mineral powder, sieving the powder with a 200-mesh sieve, and filling the powder into a sealing bag for later use;
wherein, each gram of the nano clay mineral needs 2-10 m L hydrochloric acid;
(2) synthesis of a precursor: placing the acid activated nano clay powder and the phenol derivative into a reaction kettle, adding nitric acid, stirring, sealing the reaction kettle, heating at 100-120 ℃, keeping the temperature for 1-2 hours, naturally cooling, filtering, drying a filter cake, transferring into a beaker, adding concentrated sulfuric acid and ammonium sulfate, placing into an electric heating forced air drying oven, and heating at 150-200 ℃ for 1-2 hours to obtain a sulfonated gel;
the mass ratio of the acid activated nano clay powder to the phenol derivative is 1: 20-200, 50-1000 ml of nitric acid is added into each gram of acid activated nano clay, the concentration of the nitric acid is 5 mol/L, and 1-10 ml of concentrated sulfuric acid and 0.2-5 g of ammonium sulfate are added into each gram of acid activated nano clay;
(3) fast foaming and carbonizing treatment of sulfonated gel: and placing the obtained sulfonated gel in a porcelain boat, placing the porcelain boat in an atmosphere microwave tube furnace, introducing nitrogen at the flow rate of 0.3-2.0 ml/s as protective atmosphere, heating to 800-1200 ℃, preserving heat, carbonizing for 3-5 min, and naturally cooling to finally obtain the nano-clay mineral reinforced foam carbon composite material.
The purified natural nano clay mineral in the step (1) is a purified mineral obtained by concentrating natural minerals sepiolite, attapulgite, talc or black talc through centrifugal field gravity concentration, and the content of the corresponding mineral is more than 90%; wherein, the sepiolite and the attapulgite are nano fiber structure minerals containing a large number of micropores, and the talc and the black talc are nano sheet layer structure minerals.
And (2) in the step (1), the acid activation treatment is carried out by stirring for 0.5h at the speed of 1300-2500 r/min by a stirrer, then carrying out ultrasonic dispersion for 0.5h, and then respectively stirring for 0.5h and ultrasonic treatment for 0.5 h.
The filter cake in the step (1) is rapidly activated and loosened by microwave, and the filter cake is heated and treated for 20-30 min at 200-500 ℃ by using a 1200W microwave oven to obtain activated clay mineral;
the purified natural nano clay mineral in the step (1) is one or more of sepiolite, attapulgite, talc and black talc, and the content of the mineral reaches more than 90%.
The phenolic derivative in the step (2) is hydroquinone, resorcinol, p-nitrophenol or p-nitroaniline.
And (3) the sulfonated gel is foamed and carbonized, and the temperature is raised from room temperature to the carbonization temperature by using an atmosphere microwave tube furnace, wherein the heating rate is 20-100 ℃/min.
The invention has the beneficial effects that: compared with the preparation of the carbon foam by using mesophase pitch and resin, the preparation process is simple, no foaming agent is added, and the density of the prepared carbon foam is lower than 0.02g/cm3. The natural nano clay mineral is activated, so that the structural pore canal can be dredged, an active center can be formed on the surface of the natural nano clay mineral, and the combination is facilitatedPhenolic compounds enter the inner pore channels through adsorption, and are subjected to sulfonation reaction at high temperature, and the high energy of microwaves promotes the rapid expansion of the sulfonated gel compounds, so that the preparation of the ultralight nano clay mineral reinforced composite organic carbon sponge material rich in various active functional groups is facilitated.
The natural nano clay mineral with the adsorption performance is doped into the foam carbon, so that the adsorption performance of the foam carbon can be enhanced, the mechanical stability such as strength and the like of the foam carbon can be optimized, the foam carbon is prevented from being dispersed and pulverized in the sewage treatment process, the natural loss of the adsorbent is reduced, and the adsorption and purification effects of pollutants are improved. The current situations that common high-capacity foam carbon adsorption materials are dispersed in water, difficult to recover, form secondary pollution and difficult to effectively utilize are overcome. In addition, the cheap natural nano clay mineral plays a role in supporting a pore structure, so that the wall thickness of the foam carbon is less than 100nm, the density is reduced, the pore wall is strengthened by forming stacked folds, and the specific surface area of the foam carbon is increased.
When the ultra-light foamy carbon prepared by the invention is used for treating emulsified oil wastewater, the addition amount (g) of the foamy carbon composite material is only 0.2% of the volume (ml) of wastewater for high-concentration industrial wastewater with the emulsified oil concentration up to 2000 mg/L, so that the removal rate of emulsified oil in the industrial emulsified oil wastewater can reach 99% within 30min, which is incomparable with conventional inorganic mineral adsorbing materials, inorganic polyaluminium chloride, polyferric chloride, activated carbon commonly used in water treatment, light foamy carbon and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a synergistically enhanced foamy carbon material of attapulgite and black talc prepared in example 5; wherein FIG. 1a is a photograph magnified 1500 times; FIG. 1b is a photograph magnified 5000 times;
FIG. 2 is a transmission electron micrograph of the attapulgite and black talc synergistically enhanced carbon foam material prepared in example 5.
Detailed Description
The purified natural nano clay mineral in the step (1) is a powder obtained by enriching natural minerals, namely sepiolite, attapulgite, talc or black talc, through centrifugal field gravity concentration, wherein the content of corresponding minerals reaches more than 90%; wherein, the sepiolite and the attapulgite are nano fiber structure minerals containing a large number of micropores, and the talc and the black talc are nano sheet layer structure minerals. Wherein, the natural mineral sepiolite is obtained by manufacturers: xiangtan sepiolite technologies, ltd, attapulgite: jiuzchuan nanotechnology co Ltd, talc: haicheng xufeng powder limited or black talc: guangfeng county Fangzheng non-mine development company ". The materials that can be used in the present invention are not limited thereto.
Example 1
The method comprises the following steps:
50g of purified talc is taken in a 500ml beaker, 100ml of 1 mol/L hydrochloric acid is added, the mixture is stirred for 0.5h at 1300r/min, then ultrasonic dispersion is carried out for 0.5h, stirring is carried out for 0.5h, then ultrasonic dispersion is carried out for 0.5h, suction filtration is carried out, a filter cake is heated for 20min by a 1200W microwave oven under the control of the heating temperature of 500 ℃, the filter cake is taken out, deionized water is used for repeatedly washing to be neutral, the filter cake is dried for 24h in a drying box at 70 ℃, then ball milling and crushing are carried out, and the filter cake is filled in a sealing bag for standby after being sieved by a.
Step two:
putting 1.0g of the talc powder subjected to the activation treatment obtained in the step one and 20g of p-nitrophenol into a reaction kettle, adding 50ml of nitric acid with the concentration of 5 mol/L, uniformly stirring, sealing the reaction kettle, preserving heat for 2 hours at 100 ℃, naturally cooling, filtering, transferring a filter cake into a beaker for drying, adding 1ml of concentrated sulfuric acid with the concentration of 98% and 0.2g of ammonium sulfate, and heating for 2 hours at 150 ℃ in an electrothermal blowing drying oven to obtain a sulfonated gel;
step three:
and (3) placing the sulfonated gel obtained in the step two into a porcelain boat, placing the porcelain boat into a microwave tube furnace with an atmosphere of CY-TU1400C-M of a Long Meter microwave company, introducing nitrogen at a flow rate of 0.3ml/s as a protective atmosphere, raising the temperature from room temperature to 800 ℃ at a speed of 20 ℃/min, then preserving heat, carbonizing for 5min, and naturally cooling to obtain the talc reinforced foam carbon composite material. The density is only 0.015g/cm3。
The emulsified oil-containing industrial wastewater discharged from a talc reinforced foam carbon composite material processing workshop prepared by the embodiment is filtered after the foam carbon composite material is added in an amount of 0.1g/100ml and is subjected to oscillation adsorption at 25 ℃ for 30min when the concentration of the emulsified oil in the wastewater is 2000 mg/L, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil is calculated to be 1015mg/g, and the absorbance of the filtrate is measured after the foam carbon composite material is added in an amount of 0.50g/100ml and is subjected to oscillation adsorption at 25 ℃ for 30min, and the removal rate of the emulsified oil reaches 99%.
Example 2
The method comprises the following steps:
adding 25g of purified sepiolite into a 500ml beaker, adding 250ml of 0.5 mol/L hydrochloric acid, stirring for 0.5h at 2500r/min at normal temperature, then ultrasonically dispersing for 0.5h, stirring for 0.5h, then ultrasonically dispersing for 0.5h, performing suction filtration, heating a filter cake in a 1200W microwave oven at a controlled heating temperature of 200 ℃ for 20min, taking out, repeatedly washing with deionized water to neutrality, drying in a drying box at 80 ℃ for 24h, performing ball milling and crushing, sieving with a 200-mesh sieve, and filling powder into a sealing bag for later use to obtain the activated sepiolite.
Step two:
putting 1.0g of the sepiolite powder subjected to activation treatment obtained in the step one and 200g of hydroquinone into a reaction kettle, adding 1000ml of nitric acid with the concentration of 5 mol/L, uniformly stirring, sealing the reaction kettle, preserving heat for 1.0h at 120 ℃, naturally cooling, filtering, transferring a filter cake into a beaker, adding 10ml of concentrated sulfuric acid with the concentration of 98% and 5g of ammonium sulfate, and heating for 1h at 200 ℃ in an electric heating forced air drying box to obtain sulfonated gel;
step three:
and (3) placing the sulfonated gel obtained in the step two into a porcelain boat, placing the porcelain boat into a microwave tube furnace with the atmosphere of CY-TU1400C-M of a Long Meter microwave company, introducing nitrogen at the flow rate of 2.0ml/s as protective atmosphere, raising the temperature from room temperature to 1200 ℃ at the speed of 100 ℃/min, preserving the temperature, carbonizing for 3min, and naturally cooling to obtain the sepiolite reinforced foam carbon composite material. The density is only 0.005g/cm3。
When the concentration of emulsified oil in the industrial wastewater discharged from the sepiolite reinforced foam carbon composite material processing workshop prepared by the embodiment is 2000 mg/L, when the addition amount of the sepiolite foam carbon composite material is 0.1g/100ml, after oscillation adsorption for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil reaches 1505mg/g, when the addition amount of the foam carbon composite material is 0.36g/100ml, after oscillation adsorption for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, and the removal rate of the emulsified oil reaches 99%.
Example 3
The method comprises the following steps:
taking 50g of purified attapulgite, putting the purified attapulgite in a 500ml beaker, adding 250ml of 0.8 mol/L hydrochloric acid, stirring for 0.5h at 1800r/min at normal temperature, then ultrasonically dispersing for 0.5h, stirring for 0.5h, then ultrasonically dispersing for 0.5h, suction-filtering, heating the filter cake in a 1200W microwave oven at the controlled heating temperature of 350 ℃ for 20min, taking out, repeatedly washing with deionized water to neutrality, drying in a 75 ℃ drying box for 24h, then ball-milling and crushing, sieving with a 200-mesh sieve, and putting the powder into a sealed bag for later use to obtain the activated attapulgite powder.
Step two:
mixing 1.0g of the attapulgite powder subjected to activation treatment obtained in the step one with 50g of resorcinol in a reaction kettle, adding 200ml of nitric acid with the concentration of 5 mol/L, uniformly stirring, sealing the reaction kettle, preserving heat at 115 ℃ for 1.5h, naturally cooling, filtering, transferring a filter cake into a beaker, adding 8ml of concentrated sulfuric acid with the concentration of 98% and 2.5g of ammonium sulfate, and heating for 1.5h in an electrothermal blowing drying oven at 170 ℃ to obtain sulfonated gel;
step three:
placing the sulfonated gel obtained in the step two in a porcelain boat, placing the porcelain boat in a microwave tube furnace with the atmosphere of CY-TU1400C-M of a Long instrument microwave company, introducing nitrogen at the flow rate of 1.0ml/s as protective atmosphere, raising the temperature from room temperature to 1100 ℃ at the speed of 50 ℃/min, preserving the temperature, carbonizing for 4min, and naturally cooling to obtain the sulfonated gel with the density of only 0.003g/cm3Attapulgite reinforced foam carbon composite material.
When the concentration of emulsified oil in the industrial wastewater containing emulsified oil discharged from an attapulgite reinforced foam carbon composite material purification machining workshop prepared by the embodiment is 2000 mg/L, when the addition amount of the attapulgite foam carbon composite material is 0.1g/100ml, after oscillation adsorption is carried out for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil is 1592mg/g, when the addition amount of the foam carbon composite material is 0.30g/100ml, after oscillation adsorption is carried out for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, and the removal rate of the emulsified oil reaches 99%.
Example 4
The method comprises the following steps:
50g of purified black talc is taken in a 500ml beaker, 150ml of 2.0 mol/L hydrochloric acid is added, after 2100r/min is stirred for 0.5h, ultrasonic dispersion is carried out for 0.5h, stirring is carried out for 0.5h, then ultrasonic dispersion is carried out for 0.5h, suction filtration is carried out, a filter cake is heated for 20min by a 1200W microwave oven under the control of the heating temperature of 450 ℃, taken out, repeatedly washed to be neutral by deionized water, dried for 24h in a drying box at the temperature of 80 ℃, ground by ball milling and sieved by a 200-mesh sieve to obtain activated black talc powder, and the activated black talc powder is filled in a sealed bag for standby.
Step two:
taking 1.0g of the black talc powder subjected to activation treatment obtained in the step one and 50g of p-nitroaniline into a reaction kettle, adding 150ml of nitric acid with the concentration of 5 mol/L, uniformly stirring, sealing the reaction kettle, preserving heat for 1h at 115 ℃, naturally cooling, filtering, transferring a filter cake into a beaker, adding 3ml of concentrated sulfuric acid with the concentration of 98% and 1.0g of ammonium sulfate, and heating for 1h at 180 ℃ in an electrothermal blowing drying box to obtain sulfonated gel;
step three:
placing the sulfonated gel obtained in the step two into a porcelain boat, placing into a microwave tube furnace with a type CY-TU1400C-M atmosphere of a Long instrument microwave company, introducing nitrogen at a flow rate of 1.5ml/s as a protective atmosphere, heating from room temperature to 1100 ℃ at a speed of 60 ℃/min, preserving heat, carbonizing for 3min, and naturally cooling to obtain the sulfonated gel with the density of only 0.002g/cm3The black talc of (a) reinforces the carbon foam composite.
The emulsified oil-containing industrial wastewater discharged from a foam carbon composite material purification machine processing workshop is reinforced by the black talc prepared by the embodiment, when the concentration of the emulsified oil in the wastewater is 2000 mg/L, when the addition amount of the foam carbon composite material is 0.1g/100ml, the foam carbon composite material is subjected to oscillation adsorption at 25 ℃ for 30min and then is filtered, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil is 1689mg/g, when the addition amount of the foam carbon composite material is 0.25g/100ml, the foam carbon composite material is subjected to oscillation adsorption at 25 ℃ for 30min and then is filtered, the absorbance of the filtrate is measured, and the removal rate of the emulsified oil reaches 99%.
Example 5
The method comprises the following steps:
according to the flow of the step one in the embodiment 4, the attapulgite and the black talc are respectively activated to obtain activated attapulgite and black talc powder which are sieved by a 200-mesh sieve, and the activated attapulgite and the black talc powder are filled into a sealing bag for standby.
Step two:
respectively adding 0.5g of the activated attapulgite obtained in the step one, 0.5g of black talc powder and 80g of hydroquinone into a reaction kettle, adding 250ml of nitric acid with the concentration of 5 mol/L, stirring uniformly, sealing the reaction kettle, keeping the temperature for 1h at 120 ℃, naturally cooling, filtering, transferring a filter cake into a beaker, adding 8ml of concentrated sulfuric acid with the concentration of 98% and 2.0g of ammonium sulfate, and heating for 1h at 180 ℃ in an electric heating forced air drying box to obtain the sulfonated gel.
Step three:
placing the sulfonated gel obtained in the step two in a porcelain boat, placing the porcelain boat in a microwave tube furnace with atmosphere of CY-TU1400C-M of Long instrument microwave company, introducing nitrogen at the flow rate of 0.5ml/s as protective atmosphere, heating from room temperature to 1150 ℃ at the speed of 80 ℃/min, preserving heat, carbonizing for 3min, and naturally cooling to obtain the sulfonated gel with the density of only 0.006g/cm3The attapulgite and the black talc synergistically reinforce the foamed carbon composite material.
The attapulgite and black talc reinforced foam carbon composite material prepared by the embodiment is used for purifying emulsified oil-containing industrial wastewater discharged from a mechanical cutting processing workshop, when the concentration of emulsified oil in the wastewater is 2000 mg/L, when the addition amount of the foam carbon composite material is 0.1g/100ml, after oscillation adsorption is carried out for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil reaches 1846mg/g, when the addition amount of the foam carbon composite material is 0.20g/100ml, after oscillation adsorption is carried out for 30min at 25 ℃, filtration is carried out, the absorbance of the filtrate is measured, and the removal rate of the emulsified oil reaches 99%.
FIG. 1(a) is a 1500 times magnified photograph of a foam carbon composite material synergistically enhanced by attapulgite and black talc, and when the photograph is observed in FIG. 1, the foam carbon is a composite pore structure material, wherein a large number of irregular pores are distributed in the foam carbon, the pore diameter is different from several micrometers to dozens of micrometers, and small pores are also nested in the large pores; the surface of the pore wall carbon film layer presents a large number of groove-shaped folds and textures, which are equivalent to automatically formed reinforcing ribs, so that the strength performance and the specific surface area of the foam carbon are increased, the adsorption performance of the foam carbon is enhanced, and the adsorption capacity of the foam carbon is increased.
Fig. 1(b) is a photograph of a 5000-fold enlarged attapulgite and black talc synergistically enhanced carbon foam composite material, and it can be seen from observation of fig. 2 that a skeleton carbon film layer constituting the carbon foam is very thin and less than 100nm, and is mostly in a curled shape, and forms holes and gaps which are mutually communicated and have different shapes, so that a possibility is provided for greatly reducing the density of the composite material; at the same time, some randomly dispersed filaments were also observed, which should be single dispersed attapulgite nanofibers, which provides the possibility for the minerals to increase the strength of the composite.
Fig. 2 is a transmission electron micrograph of the attapulgite and the black talc synergistic enhanced foam carbon composite material, and it can be seen from the micrograph that a few single attapulgite fibers are randomly distributed in a carbon film layer as thin as cicada wings, a single-layer carbon film is almost transparent, multiple layers are overlapped, the color is continuously deepened, particularly at folds and curls, the color change is obvious, wherein after a few dark areas are covered by a few black talc nanosheets, the color aggravated phenomenon is mainly shown because the black talc lamella has stronger ray absorption capacity than the carbon film.
Example 6
The method comprises the following steps:
according to the flow of the step one in the embodiment 4, the sepiolite powder and the talc powder are respectively subjected to activation treatment to obtain the activated sepiolite powder and talc powder which are respectively sieved by a 200-mesh sieve, and the activated sepiolite powder and talc powder are filled into a sealing bag for standby.
Step two:
respectively adding 0.5g of activated sepiolite, 0.5g of talcum powder and 100g of paranitroaniline obtained in the step one into a reaction kettle, adding 250ml of nitric acid with the concentration of 5 mol/L, stirring uniformly, sealing the reaction kettle, preserving the heat for 1h at 120 ℃, naturally cooling, filtering, transferring a filter cake into a beaker, adding 6ml of concentrated sulfuric acid with the concentration of 98% and 0.5g of ammonium sulfate, and heating for 1h at 180 ℃ in an electric heating forced air drying box to obtain the sulfonated gel.
Step three:
placing the sulfonated gel obtained in the step two into a porcelain boat, placing into a microwave tube furnace with atmosphere of CY-TU1400C-M of Long instrument microwave company, charging nitrogen at the flow rate of 1.0ml/s as protective atmosphere, heating from room temperature to 1150 ℃ at the speed of 80 ℃/min, keeping the temperature, carbonizing for 3min, and naturally cooling to obtain the sulfonated gel with the density of 0.012g/cm3The sepiolite and talc synergistically enhance the carbon foam composite.
When the concentration of the emulsified oil in the industrial wastewater containing emulsified oil discharged from a foam carbon composite material purifying and processing workshop reinforced by the sepiolite and the talc prepared by the embodiment is 2000 mg/L, the addition amount of the foam carbon composite material is 0.1g/100ml, the foam carbon composite material is filtered after being vibrated and adsorbed for 30min at 25 ℃, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil is 1326mg/g, the addition amount of the foam carbon composite material is 0.40g/100ml, and the absorbance of the filtrate is measured after being vibrated and adsorbed for 30min at 25 ℃, and the removal rate of the emulsified oil reaches 99%.
Example 7
The method comprises the following steps:
according to the flow of the step one in the embodiment 4, the attapulgite and the sepiolite are respectively subjected to activation treatment, so that activated attapulgite powder and sepiolite powder which are sieved by a 200-mesh sieve are respectively obtained, and the obtained powders are filled into a sealing bag for standby.
Step two:
respectively adding 0.5g of activated sepiolite, 0.5g of attapulgite powder and 50g of p-nitrophenol obtained in the step one into a reaction kettle, adding 150ml of nitric acid with the concentration of 5 mol/L, uniformly stirring, sealing the reaction kettle, keeping the temperature for 1h at 120 ℃, naturally cooling, filtering, transferring a filter cake into a beaker, adding 6ml of concentrated sulfuric acid with the concentration of 98% and 3.5g of ammonium sulfate, and heating for 1h at 180 ℃ in an electrothermal blowing drying box to obtain the sulfonated gel.
Step three:
putting the sulfonated gel obtained in the step two into a porcelain boat, putting the porcelain boat into a microwave tube furnace with the atmosphere of CY-TU1400C-M of a Long Meter microwave company, introducing nitrogen at the flow rate of 1.0ml/s as protective atmosphere, heating the porcelain boat from room temperature to 1150 ℃ at the speed of 80 ℃/min, preserving heat, carbonizing the porcelain boat for 3min, and naturally cooling the porcelain boat to obtain the sulfonated gel with the density of only 0.008g/cm3The sepiolite and the attapulgite are cooperated to reinforce the foam carbon composite material.
When the concentration of emulsified oil in the industrial wastewater containing emulsified oil discharged from a foam carbon composite material purification machining workshop synergistically enhanced by the sepiolite and the attapulgite prepared in the example is 2000 mg/L, the addition amount of the foam carbon composite material is 0.1g/100ml, the foam carbon composite material is subjected to oscillation adsorption for 30min at 25 ℃, then the industrial wastewater is filtered, the absorbance of the filtrate is measured, the unit adsorption amount of the foam carbon composite material to the emulsified oil is 1529mg/g, the addition amount of the foam carbon composite material is 0.30g/100ml, and after oscillation adsorption for 30min at 25 ℃, the absorbance of the filtrate is measured by filtering, and the removal rate of the emulsified oil reaches 99%.
The invention is not the best known technology.
Claims (6)
1. A preparation method of activated clay reinforced ultra-light foam carbon is characterized by comprising the following steps:
(1) activating the purified nano clay mineral, namely putting the purified natural nano clay mineral into a container, adding 0.5-2 mol/L hydrochloric acid, stirring at a high speed, performing ultrasonic dispersion, then performing stirring and ultrasonic dispersion treatment, and performing suction filtration to obtain a filter cake, performing microwave rapid activation and loosening on the filter cake, repeatedly washing the filter cake with deionized water until the filter cake is neutral, finally drying the filter cake for 24 hours in a drying oven at 70-80 ℃, performing ball milling and crushing to obtain acid-activated nano clay mineral powder, sieving the powder with a 200-mesh sieve, and filling the powder into a sealing bag for later use;
wherein, each gram of the nano clay mineral needs 2-10 m L hydrochloric acid;
(2) synthesis of a precursor: placing acid activated nano clay mineral powder and a phenol derivative into a reaction kettle, adding nitric acid, stirring, sealing the reaction kettle, heating, keeping the temperature at 100-120 ℃ for 1-2 hours, naturally cooling, filtering, drying a filter cake, transferring into a beaker, adding concentrated sulfuric acid and ammonium sulfate, placing into an electric heating forced air drying box, and heating at 150-200 ℃ for 1-2 hours to obtain a sulfonated gel;
the mass ratio of the acid activated nano clay mineral powder to the phenol derivative is = 1: 20-200, 50-1000 ml of nitric acid is added into each gram of the acid activated nano clay mineral powder, the concentration of the nitric acid is 5 mol/L, 1-10 ml of 98% concentrated sulfuric acid and 0.2-5 g of ammonium sulfate are added into each gram of the acid activated nano clay mineral powder;
(3) fast foaming and carbonizing treatment of sulfonated gel: and placing the obtained sulfonated gel in a porcelain boat, placing the porcelain boat in an atmosphere microwave tube furnace, introducing nitrogen at the flow rate of 0.3-2.0 ml/s as protective atmosphere, heating to 800-1200 ℃, preserving heat, carbonizing for 3-5 min, and naturally cooling to finally obtain the activated clay reinforced ultralight foam carbon.
2. The method for preparing activated clay reinforced ultra-light carbon foam according to claim 1, wherein the acid activation treatment in the step (1) is ultrasonic dispersion for 0.5h after stirring for 0.5h at 1300-2500 r/min by a stirrer, and then stirring for 0.5h and ultrasonic dispersion for 0.5 h.
3. The method for preparing activated clay reinforced ultra-light foam carbon according to claim 1, wherein the filter cake in step (1) is rapidly activated and loosened by microwave, and the filter cake is heated and treated for 20-30 min at 200-500 ℃ by using a 1200W microwave oven.
4. The method for preparing activated clay reinforced ultra-light foam carbon according to claim 1, wherein the natural nano clay mineral purified in the step (1) is one or more of sepiolite, attapulgite and talc, and the content of the mineral is more than 90%.
5. The method for preparing activated clay reinforced ultra-light carbon foam according to claim 1, wherein the phenolic derivative in the step (2) is hydroquinone, resorcinol or p-nitrophenol.
6. The method for preparing activated clay reinforced ultra-light foam carbon according to claim 1, wherein the rapid foaming and carbonization treatment of the sulfonated gel in step (3) is carried out by heating from room temperature to carbonization temperature in an atmosphere microwave tube furnace at a heating rate of 20-100 ℃/min.
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